Transcript Lecture19_Ch19_11140..

C1403
Lecture 19
Monday, November 14, 2005
Chapter 19
Coordination Complexes
19.1
19.2
19.3
19.4
19.5
The Formation of Coordination Complexes
Structures of Coordination Complexes
Crystal-Field Theory and Magnetic Properties
The Colors of Coordination Complexes
Coordination Complexes in Biology
Chapter 24
From Petroleum to Pharmaceuticals
24.1
24.2
24.3
Petroleum Refining and the Hydrocarbons
Functional Groups and Organic Synthesis
Pesticides and Pharmaceuticals
Chapter 25
Synthetic and Biological Polymers
25.1
25.2
25.3
Making Polymers
Biopolymers
Uses for Polymers
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The d block metal for coordination complexes with
molecules and ions
2
19.1
Coordination complexes
The electronic basis of the color of metal complexes
3
Coordination complex: A structure containing a metal
(usually a metal ion) bonded (coordinated) to a group of
surrounding molecules or ions.
Ligand (ligare is Latin, to bind): A ligand is a molecule or
ion that is directly bonded to a metal ion in a
coordination complex
A ligand uses a lone pair of electrons (Lewis base)
to bond to the metal ion (Lewis acid)
Coordination sphere: A metal and its surrounding ligands
Note: religare is Latin, to bind tightly
4
Complex ions: Three common structural types
Octahedral:
Most important
Tetrahedral
Square planar
5
The formation of a coordinate complex is a Lewis acidbase reaction
Lewis base: NH3
Lewis acid: Co3+
Coordination complex:
Lewis base coordinated
to a Lewis acid
Coordination complex:
Ligand (electron donor)
coordinated to a metal
(electron acceptor)
The number of ligand bonds to the central metal atom is
6
termed the coordination number
The basic idea is that the ligand (Lewis base) is
providing electron density to the metal (Lewis acid)
The bond from ligand to metal is covalent (shared pair), but both
electrons come from the ligand (coordinate covanent bond)
In terms of MO theory we visualize the coordination as the
transfer of electrons from the HO of the Lewis base to the LU of
the Lewis acid
Lewis base
Lewis acid
HO
LU
NH3
Co3+
7
Types of Ligands: Monodentate (one tooth) Ligands
Latin: “mono” meaning one and “dens” meaning tooth
8
Types of Ligands: Bidentate (two tooth) Ligands
Bidentate (chelates):
9
Types of Ligands: Ethylenediaminetetraacetate ion
(EDTA): a polydentate chelating ligand
Chelate from
Greek chela, “claw”
EDTA wraps around the metal ion at
all 6 coordination sites producing an
exceedingly tight binding to the
metal
10
Alfred Werner: the father of
the structure of coordination
complexes
Alfred Werner
Switzerland
University of Zurich
Zurich, Switzerland
b. 1866
(in Mulhouse, then Germany)
d. 1919
The Nobel Prize in Chemistry 1913
"in recognition of his work on the
linkage of atoms in molecules by which
he has thrown new light on earlier
investigations and opened up new fields
of research especially in inorganic
chemistry"
11
Lewis acids and bases
A Lewis base is a molecule or ion that donates a lone pair
of electrons to make a bond
Examples:
NH3
OH2
Cl
-
-
F
Electrons in the highest occupied orbital (HO) of a
molecule or anion are the best Lewis bases
A Lewis acid is a molecule of ion that accepts a
lone pair of electrons to make a bond
Examples:
+
H
3+
Co
2+
Co
n+
M
Molecules or ions with a low lying unoccupied orbital (LU)
of a molecule or cation are the best Lewis acids 12
Conventions in writing the structure of coordination
compounds:
A coordination compounds is a neutral species
consisting of a coordinate complex and uncoordinated
ions required to maintain the charge balance
Brackets [] are used to indicate all of the
composition of the coordinate complex
The symbol for the central atom metal of the
complex is first within the brackets
Species outside of the [] are not coordinated to the
metal but are require to maintain a charge balance
13
Ligand substitution reactions
For some complex ions, the coordinated ligands may
be substituted for other ligands
Complexes that undergo very rapid substitution of
one ligand for another are termed labile
Complexes that undergo very slow substitution of
one ligand for another are termed inert
[Ni(H2O)6]2+ + 6 NH3 
[Ni(NH3)6]2+ + 6 H2O (aqueous)
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Werner’s explanation of coordination complexes
Metal ions exhibit two kinds of valence: primary and
secondary valences
The primary valence is the oxidation number (positive
charge) of the metal (usually 2+ or 3+)
The secondary valence is the number of atoms that
are directly bonded (coordinated) to the metal
The secondary valence is also termed the “coordination
number” of the metal in a coordination complex
15
Example of a coordination complex: [Co(NH3)6]Cl3
What is the atomic
composition of the
complex?
What is the net charge
of the complex?
How do we know the charge
is 3+ on the metal?
[Co(NH3)6]
[Co(NH3)6]3+
3+ is required to balance
the three Cl- ions
The primary valence of [Co(NH3)6]Cl3 is 3 (charge on Co)
The secondary valence of [Co(NH3)6]Cl3 is 6 (ligands) 16
19.2
Structures of Coordination Complexes: The
ammonia complexes of Co(III) = Co3+
How did Werner deduce the structure of coordination complexes?
Composition
Ions released
Color
CoCl3.6NH3
3 “free” Cl- ions
Orange-Yellow
CoCl3.5NH3
2 “free” Cl- ions
Purple
CoCl3.4NH3
1 “free” Cl- ions
Green
CoCl3.3NH3
0 “free” Cl- ions
Green
In all of these complexes there is no free NH3
(No reaction with acid)
17
Logic: Cl- is not in coordination sphere; NH3 is in sphere
Compound 1:
CoCl3.6NH3 = [Co(NH3)6]3+(Cl-)3 = [Co(NH3)6](Cl)3
Conclude:
3 free Cl- ions, [Co(NH3)6]3+
Compound 2:
CoCl3.5NH3 = [Co(NH3)5Cl]2+(Cl-)2 = [Co(NH3)5Cl](Cl)2
Conclude:
2 free Cl- ions, [Co(NH3)5Cl]2+
Compound 3:
CoCl3.4NH3 = [Co(NH3)4Cl2]1+(Cl-) = [Co(NH3)4Cl2](Cl)
Conclude:
1 free Cl- ion, [Co(NH3)4Cl2]1+
Compound 4:
CoCl3.3NH3 = [Co(NH3)3Cl3]
No free Cl- ions
18
Coordination complexes: Three dimensional structures
CoCl3.6NH3
NH3
H3N Co NH3
H3N
NH3
NH3
Cl-
CoCl3.4NH3
Cl-
Cl
CoCl3.5NH3 H3N Co NH3
H3N
ClCl
H3N Co Cl
H3N
NH3
NH3
H3N Co NH3
H3N
NH3
Cl
Co
H3N
Bond toward you
NH3
Cl-
Cl
Cl-
NH3
Cl-
Isomers!
ClCo
NH3
Bond away from you
19
Coordination complexes: isomers
Isomers: same atomic composition, different structures
We’ll discuss the following types
of isomers:
Hydrate
Linkage
Cis-trans
Optical (Enantiomers)
20
Hydrate isomers:
Water in outer sphere (water
that is part of solvent)
Water in the inner
sphere water (water
is a ligand in the
coordination sphere
of the metal)
21
Linkage isomers
Example:
S
C
N Bonding to metal may occur at
the S or the N atom
Bonding occurs from
N atom to metal
Bonding occurs from
S atom to metal
22
Stereoisomers: geometric isomers (cis and trans)
Cl
Cl
H3N Co NH3
H3N
NH3
Cl
H3N Co Cl
H3N
NH3
NH3
Cl-
Cl-
23
Cis-trans isomers and beyond
Beyond cis and trans isomers
CoCl3.3NH3
Cl
H3N Co Cl
H3N
Cl
NH3
Cl
H3N Co Cl
H3N
NH3
Cl
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Optical isomers: enantiomers
Enantiomers are mirror images which are not superimposable
Enantiomers do not have a plane of symmetry
Any molecule which possesses a plane of symmetry is
superimposable on its mirror image
Enantiomers rotate polarized light in different directions;
therefore, enanotiomers are also termed “optical
isomers”
25
Enantiomers: non superimposable mirror images
A structure is termed chiral if it is not superimposable on
its mirror image
Structure
Mirror image
Of structure
Two chiral structures: non superimposable mirror images
26
Examples of enantiomers
NH3
H3N Co Cl
H2 O
Cl
H2O
NH3
Cl Co NH3
Cl
H2O
H2O
27
EDTA complexes are optically active
28
Chirality: the absence of a plane of symmetry
Enantiomers possible
If a molecule possess a plane of symmetry it is achiral
and is superimposible on its mirror image
Enantiomers NOT possible
NH3
Cl Co H2O
Cl
H 2O
NH3
Plane of symmetry
Achiral (one structure)
NH3
NH3
H3N Co Cl Cl Co NH3
H2 O
Cl Cl
H2O
H2O
H2O
No plane of symmetry
Chiral (two enantiomer)
29
Which are enantiomers (non-superimposable mirror images)
and which are identical (superimposable mirror images)?
30
19.3
Crystal Field Theory: Splitting of the 5 d
orbitals
Consider the response of the energy
of the d orbitals to the approach of 6
negatively charged ligands (a “crystal
field”) along the x, y and z axes of the
metal
The two d orbitals (dx2-y2 and dz2) that
are directed along the x, y and z axes
are affected more than the other
three d orbitals (dxy, dxz and dyz)
The result is that the dx2-y2 and
dz2 orbital increase in energy
relative to the dxy, dxz and dyz
orbitals (D0 is called the “crystal
field energy splitting
eg orbitals
t2g orbitals
31
Crystal field splitting of the 5 d orbitals by the “crystal field” of 6
ligands
eg orbitals
Crystal field
splitting
t2g orbitals
32
Paramagnetism and diamagnetism
Magnet off
Magnet on
Paramagnetic
Magnet on
diamagnetic
33
Crystal Field Splitting of d orbitals: high spin and low spin situations
for a d5 metal (draw the diagrams for high and low spin)
Large
splitting:
Low spin
Small
splitting:
High spin
Net spin = 0 spins
Diamagnetic
Net spin = 5 spins
Paramagnetic
34
The d electron configurations of M(II) cations of the
transition metals
Metal
Atom Configuration
Cation (II) Configuration
Valence electrons only
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
[Ar]4s23d1
[Ar]4s23d2
[Ar]4s23d3
[Ar]4s13d5
[Ar]4s23d5
[Ar]4s23d6
[Ar]4s23d7
[Ar]4s23d8
[Ar]4s23d9
[Ar]4s23d10
3d1
3d2
3d3
3d4
3d5
3d6
3d7
3d8
3d9
3d10
35
Building of weak field, high spin electron configurations
36
How many unpaired spins in Fe(CN)64- and in Fe(H2O)62+?
What is the charge of Fe in Fe(CN)64- and in Fe(H2O)62+?
Fe2+ in both cases
Fe = [Ar]3d64s2; Fe2+ = [Ar]3d6
What kind of ligands are CNand H2O?
Large splitting
Low spin
Small splitting
High spin
CN- is a strong field ligand and
H2O is a weak field ligand
Energy gap larger
than advantage due
to Hund’s rule
Energy gap small;
Hund’s rule applies
37
Complex
Valence
electrons
Ti(H2O)63+
Cr(H2O)63+
Fe(H2O)63+
Fe(CN)63Fe(H2O)62+
Fe(CN)62Ni(H2O)62+
Cu(H2O)62+
Zn(H2O)62+
3d1
3d3
3d5
3d5
3d6
3d6
3d8
3d9
3d10
Unpaired
electrons
1
3
5
1
4
0
2
1
0
Electron
configuration
(t2g)1
(t2g)3
(t2g)3(eg)2
(t2g)5
(t2g)4(eg)2
(t2g)6
(t2g)6(eg)2
(t2g)6(eg)3
(t2g)6(eg)4
Spin
configuration
()1
()3
( )()
()5
()4()2
()6
()6()2
()6()3
()6()4
38
19.4
Crystal Field Theory: The Color of Coordination
Compounds
h =
Absorption of a photon causes a
jump from a t2g to an eg orbital
The energy gap between
the eg and t2g orbitals, 0,
(the crystal field splitting)
equals the energy of a
photon:
0 = h= E
As 0, varies, h will also
vary and the color of the
compound will change
39
The spectrochemical series of color and magnetic properties:
weak field (red, high spin), strong field (violet, low spin)
A d5 electron metal ion
Strong field
Ligands (violet, low spin)
Weak field
Ligands (red, high
spin)
40
The color that we see is the color that
is not absorbed, but is transmitted.
The transmitted light is the
complement of the absorbed light.
So if red light is mainly absorbed the
color is green; if green light is mainly
absorbed, the color is red.
Numbers are nm
41
Color of complexes depend on the value of 0 = h= E
0 = h
“red
absorption”
“looks green”
“violet
absorption”
“looks yellow
42
In real systems there are
regions of different light
absorptions leading to a
wide range of colors
43
19.5
Coordination Complexes in Living Systems
Porphines, hemes, hemoglobin
Photosynthesis: electron transfer
Vitamin B12
44
Porphines and hemes: important molecules in living systems
These planar molecules have a “hole” in the center which to which a
metal can coordinate
Porphine (C20H14N4))
heme (C34H32N4O4Fe))
45
Why do we need to eat d metals?
Some critical enzymes in our cells are metalloproteins,
giant biolmolecules which contain a metal atom
These metalloproteins control key life processes such
as respiration and protect cells against disease
Hemoglobin is a metalloprotein which contains an iron
atom and transports O2 through out living systems
Vitamin B12, which prevents pernicious anemia, contains
a Co atom which gives the vitamin a red color
46
Reversible addition of O2 to hemoglobin
The mechanism by which oxygen is carried throughout
the body
47
Involved in many important biological processes,
including the production of red blood cells
Vitamin B12 (Co[C62H88N13O14P])CN
48
A very important porphine that converts solar
photons into food energy: chlorophyll
Chlorophyll (C55H72N4O5Mg)
49